EP4004109A1 - Polytéréphtalate de butylène à faible teneur en thf - Google Patents

Polytéréphtalate de butylène à faible teneur en thf

Info

Publication number
EP4004109A1
EP4004109A1 EP20743717.9A EP20743717A EP4004109A1 EP 4004109 A1 EP4004109 A1 EP 4004109A1 EP 20743717 A EP20743717 A EP 20743717A EP 4004109 A1 EP4004109 A1 EP 4004109A1
Authority
EP
European Patent Office
Prior art keywords
polybutylene terephthalate
motor vehicle
polyethylene terephthalate
parts
mass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP20743717.9A
Other languages
German (de)
English (en)
Other versions
EP4004109B1 (fr
Inventor
Matthias Bienmüller
Sebastian HARMS
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Envalior Deutschland GmbH
Original Assignee
Lanxess Deutschland GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lanxess Deutschland GmbH filed Critical Lanxess Deutschland GmbH
Publication of EP4004109A1 publication Critical patent/EP4004109A1/fr
Application granted granted Critical
Publication of EP4004109B1 publication Critical patent/EP4004109B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/30—Applications used for thermoforming
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

  • the invention relates to the use of polyethylene terephthalate for the production of polybutylene terephthalate-based motor vehicle interiors with a low TVOC content and a low tetrahydrofuran content in injection molding, TVOC standing for “Total Volatile Organic Compounds”.
  • VOC volatile organic compounds
  • a construct is used in the form of an indicator value, in which the sum of the concentrations of the individual compounds is used as an indicator for the VOC concentration in interiors and thus the TVOC value (“Total Volatile Organic Compounds”) is determined; see: B. Seifert, Bureau Rheinsblatt Passsaba - strengstik, 42, pages 270-278, Springer-Verlag 1999.
  • VVOC very / slightly volatile organic compounds
  • VOC volatile organic compounds (often abbreviated as FOV)
  • SVOC low volatile organic compounds
  • POM particle-bound organic compounds
  • polybutylene terephthalate (PBT) in the form of compounds, preferably reinforced with glass fibers is an essential plastic in the electrical engineering / electronics and automotive industries, especially the automotive industry.
  • AutomobilKONSTRUKTION 2/2011, pages 18-19 describes the use of PBT blends for filigree loudspeaker grilles and ventilation grilles in motor vehicle interiors.
  • WO 2013/020627 A1 describes functionalized interior trim components for a motor vehicle for its production as
  • PBT can also be used.
  • PBT As a semi-crystalline plastic, PBT has a narrow melting range in the range from 220 to 225 ° C. The high crystalline content enables stress-free molded parts made of PBT to be heated to below the melting temperature for a short time without deformation or damage. Pure PBT melts are thermally stable up to 280 ° C for a short time and are not subject to significant molecular degradation and do not show any significant development of gases and vapors. Like all thermoplastic polymers, however, PBT also decomposes when exposed to excessive thermal stress, especially when overheated or when cleaned by burning off. This forms gaseous decomposition products. The decomposition accelerates above about 300 ° C, initially mainly tetrahydrofuran (THF) and water.
  • THF tetrahydrofuran
  • THF is already formed during the production of the PBT by intramolecular condensation from the monomer 1,4-butanediol (BDO).
  • BDO monomer 1,4-butanediol
  • the reaction can be catalyzed both by the terephthalic acid (PTA) used and by the titanium-based catalyst mostly used to produce the PBT.
  • PTA terephthalic acid
  • DMT dimethyl terephthalate
  • THF is continuously reproduced in the PBT melt at high temperatures. This process, also described as "back-biting", takes place at the BDO end groups. Like the THF formation from BDO monomer, this reaction is an intramolecular condensation which leads to the undesired by-product tetrahydrofuran.
  • the THF replication from the polymer in the melt is also catalyzed by both acid end groups (PTA) and the existing catalyst (titanium-based).
  • VDA Association of Automobile Manufacturers
  • VDA 278 followed in 2002, which is based on a dynamic headspace method, the so-called thermal desorption, and specifies both the volatile organic compounds (VOC) and the condensable components (Fog value).
  • VOC volatile organic compounds
  • Fog value condensable components
  • EP 1 070 097 A1 (WO99 / 50345 A1) Addition of polyacrylic acid to polyesters based on lactic acid during polymerization to deactivate Sn or Sb catalysts used in PBT production;
  • EP 1 999 181 A2 (W 02007/111890 A2) Addition of a phosphorus-containing component to deactivate the titanium catalyst used in PBT production.
  • the emission values given in EP 1 999 181 A2 are percentages, i.e. they are not absolute values and, moreover, could be improved;
  • EP 2 427 511 B1 addition of a styrene-acrylic polymer e.g. Joncryl®ADR-4368
  • a styrene-acrylic polymer e.g. Joncryl®ADR-4368
  • EP 2 816 081 A1 Addition of a chelating agent from the group of sodium hypophophosphite, nitrilotriacetic acid, disodium salt of EDTA, diammonium salt of EDTA, EDTA, diethylenetriaminepentaacetic acid, hydroethylenediamine triacetic acid, ethylenediaminedisuccinic acid and in particular 1,3-propylenediamine;
  • EP 3 287 493 A1 discloses in the examples injection molding compositions comprising 100 parts by weight of polybutylene terephthalate, 8.4 and 8.7 parts by weight of polyethylene terephthalate and 50 and 52 parts by weight of silane-coated glass fibers;
  • JP 2016 145333 A teaches in Example 1 an injection molding composition comprising 100 parts by weight of polybutylene terephthalate, approx. 13 parts by weight of polyethylene terephthalate and glass fibers;
  • EP 3 004 242 A1 (WO2014 / 195176 A1) Addition of sodium hypophosphite or epoxy-functionalized styrene-acrylic acid polymer for the production of PBT molded parts with less than or equal to 100 pgC / g TVOC according to VDA277.
  • the object of the present invention was to provide PBT-based compounds for processing in injection molding for motor vehicle interiors with an optimized TVOC value and THF outgassing behavior, with the outgassing behavior measured on the injection molded part having a TVOC ⁇ 50pgC / g according to VDA 277 and a VOC THF ⁇ 5 pg / g according to VDA 278 within the meaning of the Association of the Automotive Industry (VDA).
  • VDA Association of the Automotive Industry
  • PET polyethylene terephthalate
  • the addition of the PET to be used according to the invention leads to a significant reduction in the total TVOC emission and the THF emission TVOCTHF or VOC T HF that goes beyond the dilution effect of the PET.
  • the measurable TVOC value on the component manufactured by injection molding according to VDA 277 fell from an average of 90 to 100 pgC / g to below 45 pgC / g.
  • the THF content fell from an average of 80 - 85 pgC / g to below 30 pgC / g.
  • VOC TH F according to VDA 278 was reduced by the presence of PET from an average of 6 to 7 pg / g to below 2 pg / g. All information here relates to the state defined in the corresponding test specification, as described below.
  • the invention relates to motor vehicle interiors containing compounds based on PBT and PET, 5 to 30 parts by mass of PET being used in the compounds for 100 parts by mass of PBT, preferably with a TVOC ⁇ 50 pgC / g to be determined according to VDA 277 and a VOC THF ⁇ to be determined according to VDA 278 5 pg / g and with the proviso that PET and PBT are not present as a copolymer, but as a mixture.
  • the invention also relates to the use of PET for the production of PBT-based compounds for processing by injection molding into components in motor vehicle interiors with a TVOC ⁇ 50 pg / g to be determined according to VDA 277 and a VOC TH F ⁇ 5 pg / g to be determined according to VDA 278, 5 to 30 parts by mass of PET are used for 100 parts by mass of PBT, with the proviso that PET and PBT are not present as a copolymer but as a mixture.
  • the invention finally relates to a method for reducing the THF content in PBT-based motor vehicle interiors, characterized in that, in their manufacture by injection molding, polybutylene terephthalate-based compounds with at least polyethylene terephthalate are used, in which there are 5 to 30 parts by mass of polyethylene terephthalate per 100 parts by mass of polybutylene terephthalate, with the proviso that polybutylene terephthalate and polyethylene terephthalate are not present as a copolymer, but as a mixture.
  • MFR Melt Mass-Flow Rate
  • MFI Melt Flow Index
  • VDA 277 reference is made in the context of the present invention to the version from 1995; with regard to VDA 278, reference is made to the version from October 2011.
  • VDA 277 stipulates that samples must be taken immediately after receipt of the goods or in a condition that corresponds to this.
  • VDA 278 regulates that the material to be examined is usually packed airtight in aluminum-coated PE bags within 8 hours after its production and the sample must be sent to the laboratory immediately. Before the measurement, the samples should be conditioned for 7 days in a standard climate (23 ° C, 50% rel. Humidity).
  • TVOC THF determined in the context of the present invention was determined using the same method as TVOC in accordance with VDA277, the evaluation relating to the individual substance THF.
  • TVOC THF therefore makes a statement about the THF emission behavior of a sample in the context of the present invention.
  • VOCi HF is determined using the same method as VOC according to VDA278, the evaluation referring to the individual substance THF.
  • VOCTHF therefore makes a statement about the THF emission behavior of a sample.
  • compounding takes place in a twin-screw extruder with a vacuum degassing zone, preferably a co-rotating twin-screw extruder with a vacuum degassing zone.
  • Compounding includes the process operations conveying, melting, dispersing, mixing, degassing and pressure build-up.
  • the product of a compounding is a compound.
  • the purpose of compounding is to make the plastic raw material, in the case of the present invention, the PBT resulting from the reaction of butanediol with PTA or DMT, a plastic molding compound with the best possible properties for processing and subsequent use, here in the form of a vehicle interior according to VDA 277 and VDA 278.
  • the tasks of compounding are changing the particle size, incorporating additives and removing components. Since many plastics are produced in the form of powders or coarse resins and are therefore useless for processing machines, especially injection molding machines, the further processing of these raw materials is particularly important.
  • the finished mixture of polymer, here PBT, and additives is called molding compound.
  • the individual components of the molding compositions can be in various aggregate states, such as powder, granular or liquid / flowable.
  • the aim of using a compounder is to mix the components as homogeneously as possible into the molding compound.
  • the following additives are preferably used in compounding: antioxidants, lubricants, impact modifiers, antistatic agents, fibers, talc, barium sulfate, chalk, thermal stabilizers, iron powder, light stabilizers, release agents, mold release agents, Nucleating agents, UV absorbers, flame retardants, PTFE, glass fibers, soot, glass spheres, silicone.
  • Components can also be removed during compounding. Two components are preferably removed, moisture components (dehumidification) or low-molecular components (degassing).
  • moisture components dehumidification
  • low-molecular components degassing
  • the THF obtained as a by-product in the synthesis of the PBT is removed from the molding compound by applying a vacuum.
  • Mixing and granulating are two essential steps in compounding.
  • mixing a distinction is made between distributive mixing, i.e. the even distribution of all particles in the molding compound, and dispersive mixing, i.e. the distribution and comminution of the components to be mixed.
  • the mixing process itself can be carried out either in the viscous phase or in the solid phase.
  • the distributive effect is preferred, since the additives are already in comminuted form. Since mixing in the solid phase is rarely sufficient to achieve good mixing quality, the term premixing is often used. The premix is then mixed in the melt state.
  • Viscous mixing generally consists of five steps, melting the polymer and the additives (the latter if possible), dividing the solid agglomerates (agglomerates are agglomerations), wetting the additives with polymer melt, distributing the components evenly and separating them unwanted constituents, preferably air, moisture, solvents and, in the case of the PBT to be considered according to the invention, the THF.
  • the heat required for viscous mixing is essentially caused by the shear and friction of the components. In the case of the PBT to be considered according to the invention, viscous mixing is preferably used.
  • a heating / cooling mixer system is used here.
  • the material to be mixed is mixed in the heating mixer and then flows into a cooling mixer, where it is temporarily stored. This is how dry blends are made.
  • Co-rotating twin-screw extruders / compounding extruders are preferably used for compounding PBT.
  • the task of a compounder / extruder is to draw in the plastic mass supplied to it, to compress it, to plasticize and homogenize it at the same time while supplying energy, and to compress it under pressure feed the profiling tool.
  • Twin-screw extruders with a pair of co-rotating screws are suitable for processing (compounding) plastics, especially PBT, due to their good mixing.
  • a co-rotating twin screw extruder is divided into several process zones. These zones are linked to one another and cannot be viewed independently of one another. For example, fibers are incorporated into the melt not only in the predetermined dispersion zone, but also in the discharge zone and in other screw flights.
  • the plastic Since most processors need the plastic, in this case the PBT, as granules, granulation is playing an increasingly important role. A basic distinction is made between hard work and cold tee. Depending on the processing, this results in different grain shapes.
  • the plastic In the case of diligence, the plastic is preferably obtained in the form of pearls or lentil grains. In the case of cold cuts, the plastic is preferably obtained in cylinders or cube shapes.
  • the extrusion strand When working hard, the extrusion strand is chopped off directly after a nozzle by a rotating knife overflowing with water.
  • the water prevents the individual granules from sticking together and cools the material. Most of the time water is used for cooling, but air can also be used. The selection of the right coolant therefore depends on the material.
  • the disadvantage of water cooling is that the granulate has to be dried afterwards.
  • cold cutting the strands are first drawn through a water bath and then cut to the desired length by a rotating knife roller (granulator) in the solid state. In the case of the PBT to be used according to the invention, cold reduction is used.
  • the present invention preferably relates to vehicle interiors obtainable by injection molding containing compounds based on PBT and at least PET in which 5 to 30 parts by mass of PET are used for 100 parts by mass of PBT, with a TVOC to be determined according to VDA 277 ⁇ 50 pgC / g and a VOC to be determined according to VDA 278 TH F ⁇ 5 pg / g.
  • a twin-screw extruder is preferably used for compounding the PBT for motor vehicle interiors.
  • the job of a compounder in particular in the form of a twin screw extruder, consists in drawing in the plastic mass fed to it, compressing it, simultaneously plasticising and homogenising it while supplying energy, and feeding it to a profiling tool under pressure.
  • Twin-screw extruders to be used with preference according to the invention are suitable for compounding PBT, preferably for incorporating at least one filler into the PBT.
  • Twin-screw extruders to be used according to the invention are known to the person skilled in the art, for example from DE 203 20 505 U1, and are preferably offered by Coperion Werner & Pfleiderer GmbH & Co. KG, Stuttgart.
  • a twin-screw extruder to be used according to the invention is divided into several process zones. These zones are linked to one another and cannot be viewed independently of one another.
  • the twin-screw extruder is preferably operated with a throughput in the range from 3 to 10 t / h (tons per hour).
  • a twin-screw extruder with a screw diameter in the range from 60 mm to 100 mm.
  • a pressure in the range of 300 +/- 50 mbar is preferably applied to the vacuum degassing zone of the twin-screw extruder.
  • Pressure data in the context of the present invention are negative pressures or vacuum and relate to the respective prevailing atmospheric pressure (relative pressure).
  • vacuum is defined as “the state of a gas when the pressure of the gas and thus the particle number density in a container is lower than outside, or when the pressure of the gas is lower than 300 mbar, i. H. lower than the lowest atmospheric pressure occurring on the earth's surface ”.
  • Vacuum pumps are preferably used in the vacuum degassing zone of the twin-screw extruder to achieve a pressure of 300 +/- 50 mbar, which is aimed at according to the invention from the range of rotary vane pumps, liquid ring pumps, scroll pumps,
  • Roots pumps and screw pumps are used. See: https: //www.pfeiffer- vacuum.com/de/know-how/einfuehrung-in-die-vakuumtechnik/all Zelles/vakuum- definition /
  • the compounding section of a twin-screw extruder to be used according to the invention comprises feed device, feed zone, melting zone, atmospheric degassing zone, at least one filler feed zone, filler mixing zone, backflow zone, vacuum degassing zone, pressure build-up Zone and discharge zone.
  • the vacuum degassing zone is located in the last third of the compounding section, the last third relating to the total length of the twin-screw extruder.
  • the total length of the twin screw extruder is defined as the distance between the start of the feed zone and the end of the discharge zone.
  • the last third expressly includes the discharge zone.
  • the result of compounding PBT with PET, preferably in a twin-screw extruder, is a THF-reduced PBT compound in granulate form with a very low THF content.
  • This THF content is so low that even after processing the granulate in injection molding, whereby decomposition processes lead to a THF replica, products, especially vehicle interiors, can still be injection molded which have a TVOC ⁇ 50 pgC / g to be determined according to VDA 277 and one according to VDA 278 have to be determined VOC TH F ⁇ 5 pg / g.
  • PBT to be used according to the invention [CAS No. 24968-12-5] is available, for example, under the brand Pocan® from LANXESS Deutschland GmbH, Cologne.
  • the viscosity number of the PBT to be used according to the invention to be determined in accordance with DIN EN ISO 1628-5 is preferably in a 0.5% strength by weight solution in a phenol / o-dichlorobenzene mixture (weight ratio 1: 1 at 25 ° C.) a range from 50 to 220 cm 3 / g, particularly preferably in the range from 80 to 160 cm 3 / g; Please refer:
  • PBT whose carboxyl end group content to be determined by titration methods, in particular potentiometry, is up to 100 meq / kg, preferably up to 50 meq / kg and in particular up to 40 meq / kg polyester.
  • Such polyesters can be produced, for example, by the method of DE-A 44 01 055.
  • the content of carboxyl end groups (CEG) in the PBT to be used according to the invention was determined in the context of the present invention by potentiometric titration of the acetic acid released when a sample of the PBT dissolved in nitrobenzene was reacted with a defined excess of potassium acetate.
  • Polyalkylene terephthalates are preferably produced with Ti catalysts.
  • a PBT to be used according to the invention preferably has a Ti content of ⁇ 250 ppm, particularly preferably ⁇ 200 ppm, particularly preferably ⁇ 150 ppm, to be determined by means of X-ray fluorescence analysis (XRF) according to DIN 51418.
  • XRF X-ray fluorescence analysis
  • Such polyesters are preferably produced by the method in DE 101 55 419 B4, the content of which is hereby fully included.
  • PET Polyethylene terephthalate
  • the PET (CAS No. 25038-59-9) to be used according to the invention for the reduction of THF in PBT as a mixing partner is a reaction product of an aromatic dicarboxylic acid or its reactive derivatives, preferably dimethyl esters or anhydrides, and an aliphatic, cycloaliphatic or araliphatic diol and mixtures of these Educts.
  • the preferred PET to be used is produced from terephthalic acid (or its reactive derivatives) and the aliphatic diol with 2 carbon atoms by known methods (Kunststoff-Handbuch, Vol. VIII, pp. 695-703, Karl-Hanser-Verlag, Kunststoff 1973) .
  • the PET is preferably compounded in via at least one filler feed zone in the compounding section of the twin-screw extruder.
  • Preferred PET contains at least 80 mol%, particularly preferably at least 90 mol%, based on the dicarboxylic acid, terephthalic acid residues and at least 80 mol%, preferably at least 90 mol%, based on the diol component, ethylene glycol residues.
  • PET which is preferably used can contain up to 20 mol% residues of other aromatic dicarboxylic acids with 8 to 14 carbon atoms or residues of aliphatic dicarboxylic acids with 4 to 12 carbon atoms, particularly preferably residues of phthalic acid, isophthalic acid, naphthalene-2,6- dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid, or cyclohexanedicarboxylic acid.
  • PET to be used with preference can contain up to 20 mol% of other aliphatic diols with 3 to 12 carbon atoms or cycloaliphatic diols with 6 to 21 carbon atoms in addition to ethylene glycol residues contain.
  • Residues of propanediol-1,3, 2-ethylpropanediol-1,3, neopentyl glycol, pentanediol-1,5, hexanediol-1,6, 3-methylpentanediol-2,4, 2-methylpentanediol-2,4,2, are particularly preferred , 2,4-trimethylpentanediol-1, 3, 2,2,4-trimethylpentanediol-1, 6, 2-ethylhexanediol-1, 3, 2,2-diethylpropanediol-1, 3, hexanediol-2,5, 1, 4 -Di- (ß-hydroxyethoxy) -benzen
  • the PET to be used according to the invention as a mixing partner can be branched by incorporating relatively small amounts of 3- or 4-valent alcohols or 3- or 4-basic carboxylic acids, as described, for example, in DE-A 19 00 270.
  • Preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and trimethylolpropane and pentaerythritol.
  • PET to be used as a mixing partner of the PBT preferably has an intrinsic viscosity in the range from about 30 cm 3 / g to 150 cm 3 / g, particularly preferably in the range from 40 cm 3 / g to 130 cm 3 / g, particularly preferably in the range from 50 cm 3 / g to 100 cm 3 / g, each measured in analogy to ISO1628-1 in phenol / o-dichlorobenzene - 1: 1 parts by weight - at 25 ° C. using an Ubbelohde viscometer. To measure the viscosity, the material is dried to a maximum moisture content of 0.02%, determined using the Karl Fischer method known to the person skilled in the art, in a commercially available circulating air dryer at 120 ° C.
  • At least one filler is compounded in via at least one filler feed zone in the compounding section of the twin-screw extruder.
  • compounds according to the invention preferably contain 0.001 to 70 parts by mass, particularly preferably 5 to 50 parts by mass, very particularly preferably 9 to 48 parts by mass of at least one filler, each based on 100 parts by mass of polybutylene terephthalate.
  • Fillers to be used according to the invention are preferably selected from the group consisting of talc, mica, silicate, quartz, titanium dioxide, wollastonite, kaolin, kyanite, amorphous silicas, magnesium carbonate, chalk, feldspar, barium sulfate, glass spheres and fibrous fillers, especially glass fibers or carbon fibers. Glass fibers are particularly preferably used.
  • cut fibers also known as short fibers, with a length in the range from 0.1 to 1 mm
  • long fibers with a length in the range of 1 to 50mm
  • continuous fibers with a length L> 50mm.
  • Short fibers are used in injection molding technology and can be processed directly with an extruder.
  • Long fibers can also be processed in extruders. They are widely used in fiber spraying.
  • Long fibers are often mixed with thermosetting plastics as fillers.
  • Continuous fibers are used as rovings or fabrics in fiber-reinforced plastics. Products with continuous fibers achieve the highest levels of rigidity and strength. Milled glass fibers are also available, the length of which after milling is typically in the range from 70 to 200 pm.
  • cut long glass fibers with an initial length in the range from 1 to 50 mm, particularly preferably in the range from 1 to 10 mm, very particularly preferably in the range from 2 to 7 mm, are used as filler.
  • the initial length denotes the average length of the glass fibers as they are present before the compounds according to the invention are compounded to form a molding material according to the invention.
  • the fibers to be used as fillers preferably glass fibers, can, due to the compounding in the product, have a smaller d90 or d50 value than the originally used fibers or glass fibers.
  • the arithmetic mean of the fiber length or glass fiber length after processing is often only in the range of 150 gm and 300 gm, which can be determined using laser diffractometry in accordance with ISO 13320.
  • the determination of the fiber length and fiber length distribution or glass fiber length and glass fiber length distribution takes place within the scope of the present invention in the case of processed fibers or glass fibers according to ISO 22314, which initially provides for the samples to be incinerated at 625 ° C.
  • the ash is then placed on a slide covered with demineralized water in a suitable crystallizing dish and the ash is distributed in the ultrasonic bath without the effect of mechanical forces.
  • the next step involves drying in an oven at 130 ° C and then using light microscopic images to determine the fiber length. For this purpose, at least 100 glass fibers are measured from three recordings, so that a total of 300 glass fibers are used to determine the length.
  • l c and s are special parameters of the normal distribution; l c is the mean value and s the standard deviation (see: M. Schossig,
  • the glass fibers [CAS No. 65997-17-3)] to be preferably used as filler according to the invention preferably have a fiber diameter in the range from 7 to 18 ⁇ m, particularly preferably in the range from 9 to 15 ⁇ m, thanks to at least one possibility available to the person skilled in the art is to be determined, in particular to be determined by g-X-ray computed tomography in analogy to "Quantitative measurement of fiber lengths and distribution in fiber-reinforced plastic parts by means of g-X-ray computer tomography", J. K ⁇ STNER, et al. DGZfP Annual Conference 2007 - Lecture 47.
  • the glass fibers to be preferably used as fillers are preferably added as cut or ground glass fibers.
  • the fillers preferably glass fibers
  • the fillers are equipped with a suitable size system or a flaft mediator or flaft mediator system.
  • a sizing system or a flake mediator based on silane is preferably used.
  • Particularly preferred flaft promoters based on silane for the treatment of the glass fibers preferably to be used as filler are silane compounds of the general formula (I)
  • X is NH 2 , carboxyl, HO or 2 2 , q is an integer from 2 to 10, preferably 3 to 4, r is an integer from 1 to 5, preferably 1 to 2 and k is is an integer from 1 to 3, preferably 1.
  • adhesion promoters are silane compounds from the group aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl or a carboxyl group as substituent X, with carboxyl groups being particularly preferred.
  • the adhesion promoter preferably the silane compounds of the formula (I)
  • the adhesion promoter is preferably used in amounts of 0.05 to 2% by weight, particularly preferably in amounts of 0.25 to 1.5% by weight. -% and very particularly preferably in amounts of 0.5 to 1% by weight, each based on 100% by weight of the filler, used.
  • the glass fibers that are preferably to be used as fillers can be shorter than the glass fibers originally used, due to the processing into the compound or the product in the compound or in the product.
  • the arithmetic mean value of the glass fiber length to be determined by means of high-resolution X-ray computer tomography is often only in the range of 150 gm to 300 gm after processing.
  • glass fibers are manufactured using the melt spinning process (nozzle drawing, rod drawing and nozzle blowing processes).
  • the hot glass mass flows through hundreds of nozzle holes in a platinum spinning plate using gravity.
  • the filaments can be pulled in unlimited lengths at a speed of 3 - 4 km / minute.
  • E-glass the most widely used material with an optimal price-performance ratio (E-glass from R&G)
  • E-glass fibers have become the most important for plastic reinforcement.
  • E stands for electrical glass, as it was originally mainly used in the electrical industry.
  • glass melts are made from pure quartz with additives from limestone, kaolin and boric acid. In addition to silicon dioxide, they contain different amounts of various metal oxides.
  • the composition determines the properties of the products.
  • at least one type of glass fibers from the group E-glass, H-glass, R, S-glass, D-glass, C-glass and quartz glass is used, particularly preferably glass fibers made of E-glass.
  • Glass fibers made from E-glass are the most widely used reinforcement material.
  • the strength properties correspond to those of metals (e.g. aluminum alloys), with the specific gravity of laminates containing E-glass fibers being lower than that of metals.
  • E-glass fibers are incombustible, heat-resistant up to approx. 400 ° C and resistant to most chemicals and weather conditions.
  • platelet-shaped mineral fillers are particularly preferably used as fillers.
  • a platelet-shaped, mineral filler is understood to mean at least one mineral filler with a strongly pronounced platelet-shaped character from the group of kaolin, mica, talc, chlorite and adhesions such as chlorite talc and plastorite (mica / chlorite / quartz). Talc is particularly preferred.
  • the platelet-shaped, mineral filler preferably has a length: diameter ratio to be determined by means of high-resolution X-ray computer tomography Range from 2: 1 to 35: 1, particularly preferably in the range from 3: 1 to 19: 1, particularly preferably in the range from 4: 1 to 12: 1.
  • the mean particle size of the platelet-shaped mineral fillers to be determined by means of high-resolution X-ray computer tomography is preferably less than 20 ⁇ m, particularly preferably less than 15 ⁇ m, particularly preferably less than 10 ⁇ m.
  • d90 values their determination and their significance, reference is made to Chemie Ingenieurtechnik (72) pp. 273-276, 3/2000, Wiley-VCH Verlags GmbH, Weinheim, 2000, according to which the d90 value is the particle size below 90% of which are the amount of particles.
  • the non-fibrous and non-foamed ground glass is of particulate, non-cylindrical shape and has a length to thickness ratio of less than 5, preferably less than 3, particularly preferably less than 2, to be determined by means of laser diffractometry in accordance with ISO 13320 of course excluded.
  • the non-foamed and non-fibrous ground glass which is particularly preferred as a filler, is also characterized in that it does not have the typical glass geometry of fibrous glass with a cylindrical or oval cross-section with a length to diameter ratio (L / D Ratio) greater than 5.
  • the non-foamed and non-fibrous ground glass to be used particularly preferably as filler according to the invention is preferably obtained by grinding glass with a mill, preferably a ball mill, and particularly preferably with subsequent sifting or sieving.
  • Preferred starting materials for the grinding of the non-fibrous and non-foamed, ground glass to be used as a filler in one embodiment are also glass waste, such as those found in the production of glass products as an undesired by-product and / or as a main product that does not meet specifications (so-called off-spec goods). attack.
  • the glass can be colored, with non-colored glass being preferred as the starting material for use as a filler.
  • Long glass fibers based on E-glass preferably with an average length d50 of 4.5 mm, such as are available, for example, as CS 7967 from LANXESS GmbH, Cologne, are particularly preferred according to the invention.
  • additives can be added to the PBT in a preferred embodiment.
  • Additives to be used with preference according to the invention are stabilizers, in particular UV stabilizers, thermal stabilizers, gamma radiation stabilizers, also antistatic agents, elastomer modifiers, flow aids, mold release agents, flame retardants, emulsifiers, nucleating agents, plasticizers, lubricants, dyes, pigments and additives to increase electrical conductivity.
  • motor vehicle interior equipment relates to all injection molded parts that are not part of the outer surface of a motor vehicle or that do not have an area portion on the outer surface of a motor vehicle.
  • Injection molded parts to be produced according to the invention for a motor vehicle interior are, in addition to the components described at the beginning in the prior art, preferably panels, plugs, electrical components or electronic components. These are installed in increasing numbers in the interior of today's automobiles in order to enable the increasing electrification of many components, in particular vehicle seats or infotainment modules. Furthermore, PBT-based components are often used in automobiles for functional parts that are subject to mechanical stress.
  • the present invention preferably relates to motor vehicle interiors containing compounds based on PBT mixed with PET and at least one filler, preferably glass fibers, with 5 to 30 parts by mass of PET in the compounds, preferably 10 to 25 parts by mass of PET, particularly preferably 12 to 17 parts by mass of PET and 0.001 to 70 parts by mass, particularly preferably 5 to 50 parts by mass, very particularly preferably 9 to 48 parts by mass of filler are used, preferably with a TVOC ⁇ 50 pgC / g to be determined according to VDA 277 and a VOC TH F to be determined according to VDA 278 ⁇ 5 pg / g.
  • PET optionally at least one filler, in particular talc or glass fibers, and optionally at least one further additive, in particular thermal stabilizer, mold release agent or pigment, to the PBT melt, incorporating it and mixing it;
  • Processes according to the invention for the production of motor vehicle interiors by injection molding are used at melt temperatures in the range from 160 to 330 ° C., preferably in the range from 190 to 300 ° C. and optionally additionally at pressures of a maximum of 2500 bar, preferably at pressures of a maximum of 2000 bar, particularly preferably Pressures of a maximum of 1500 bar and very particularly preferably at pressures of a maximum of 750 bar.
  • the PBT-based compounds or compounds according to the invention are characterized by particular melt stability, whereby the person skilled in the art understands melt stability in the context of the present invention as meaning that even after residence times> 5 min, significantly above the melting point of the molding compound of> 260 ° C. ISO 1 133 (1997) to be determined melt viscosity is observed.
  • the injection molding process is characterized in that the raw material in the form of the compound to be used according to the invention, preferably in granulate form, is melted (plasticized) in a heated cylindrical cavity and undergoes it as an injection compound Pressure is fed into a temperature-controlled cavity of a profiling tool.
  • the raw materials used are compounds according to the invention, which have preferably already been processed into a molding compound by compounding in the compounder, preferably under vacuum at a pressure of 300 +/- 50 mbar, and these in turn have preferably been processed into granules. In one embodiment, however, granulation can be dispensed with and the molding compound can be fed directly under pressure to a profiling tool. After the molding compound injected into the temperature-controlled cavity has cooled (solidified), the injection-molded part is removed from the mold.
  • motor vehicle interiors are obtained which have a TVOC ⁇ 50 pg / g to be determined according to VDA 277 and a VOCTHF ⁇ 8 pg / g to be determined according to VDA 278.
  • polybutylene terephthalate which has a weight ratio of 0.5% by weight solution at 25 ° C. in a phenol / o-dichlorobenzene mixture. 1: 1 according to DIN EN ISO 1628-5 to be determined viscosity number in a range from 50 to 220 cm 3 / g.
  • the polybutylene terephthalate preferably has a Ti content of ⁇ 250 ppm, to be determined by means of X-ray fluorescence analysis (XRF) according to DIN 51418.
  • XRF X-ray fluorescence analysis
  • the polyethylene terephthalate to be used in the process according to the invention preferably contains at least 80 mol%, based on the dicarboxylic acid, terephthalic acid residues and at least 80 mol%, based on the diol component, ethylene glycol residues.
  • polyethylene terephthalate with an intrinsic viscosity in the range from approx. 30 cm3 / g to 150 cm 3 / g is preferably measured in analogy to ISO1628-1 in phenol / o-dichlorobenzene - 1: 1 parts by weight - at 25 ° C used by means of an Ubbelohde viscometer.
  • At least one filler is preferably used in amounts in the range from 0.001 to 70 parts by mass based on 100 parts by mass of polybutylene terephthalate.
  • the filler to be used is treated with a silane-based adhesion promoter of the general formula (I)
  • X is NH 2 -, carboxyl, HO- or, q is an integer from 2 to 10, r is an integer from 1 to 5 and k is an integer from 1 to 3.
  • Motor vehicle interior fittings are preferably obtained according to the method according to the invention, in particular panels, plugs, electrical components or electronic components.
  • the VOC value was determined by weighing 20 mg of a sample in accordance with the regulation according to VDA 278 into a thermal desorption tube for GERSTEL-TD 3.5+ with a frit from Gerstel (020801-005-00). This was heated to 90 ° C for 30 min in a helium stream and the substances desorbed in the process were frozen out in a downstream cold trap at -150 ° C. After the desorption time had elapsed, the cold trap was quickly heated to 280 ° C. and the substances collected were separated by chromatography (Agilent 7890B GC). The detection was carried out using an Agilent 5977B MSD. The evaluation was carried out semi-quantitatively using a toluene calibration.
  • the result was determined in pg / g.
  • the limit value not to be exceeded in the context of the present invention was 100 pg / g total VOC or 5 pg / g THF.
  • the analysis was based on the VDA 278 test specification.
  • PBT Polybutylene terephthalate
  • PET Polyethylene terephthalate
  • the compounder used was a ZSK 92 twin-screw extruder from Coperion.
  • the compounder was operated with a melt temperature of approx. 270 ° C. and a throughput of 4 tons per hour and at a pressure of 300 +/- 50 mbar.
  • the strands were cooled in a water bath, dried on a ramp in a stream of air and then dry granulated.
  • a compound based on a PBT molding compound containing 50 parts by mass of cut glass fibers and 15 parts by mass of PET per 100 parts by mass of PBT was used.
  • the PBT used here had a TVOC value of 170 pgC / g determined according to VDA 277.
  • the compounded material was then dried for 4 hours at 120.degree. C. in a dry air dryer and under standard conditions (260.degree. C. melt temperature, 80.degree
  • the compounder used was a ZSK 92 twin-screw extruder from Coperion.
  • the compounder was operated with a melt temperature of approx. 270 ° C. and a throughput of 4 tons per hour and at a pressure of 300 +/- 50 mbar.
  • the strands were cooled in a water bath, dried on a ramp in a stream of air and then dry granulated.
  • a compound based on a PBT molding compound containing 43.3 mass fractions of chopped glass fibers was used.
  • the PBT used here had a TVOC value of 170 pgC / g, determined according to VDA 277.
  • the compounded material was dried for 4 hours at 120 ° C. in a dry air dryer and under standard conditions (260 ° C. melt temperature, 80 ° C. mold temperature) in
  • the test results shown in Table 2 show that the addition of 15 parts by mass of PET to 100 parts by mass of PBT in the example according to the invention leads to a significant reduction in the amount of THF and thus the total emission.
  • the extent of the reduction with -64.5% TVOC (33.8 compared to 95.2) and -65.1% TVOCTHF (28.8 compared to 82.5) and -73.3% VOC TH is particularly surprising F (1.6 compared to 6.0) on the component, which goes well beyond the dilution effect of the PBT by the PET. This influence on the TVOC and the formation of THF from PBT during processing was not to be expected by the person skilled in the art, since the person skilled in the art did not expect any reactive effect from the PET.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne l'utilisation de polytéréphtalate d'éthylène pour produire des garnitures intérieures de véhicule à moteur à base de polytéréphtalate d'éthylène ayant une faible teneur en TVOC (composés organiques volatils totaux) et une faible teneur en tétrahydrofurane dans la garniture moulée par injection.
EP20743717.9A 2019-07-29 2020-07-27 Téréphtalate de polybutylène à faible teneur en thf Active EP4004109B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP19188765 2019-07-29
PCT/EP2020/071156 WO2021018848A1 (fr) 2019-07-29 2020-07-27 Polytéréphtalate de butylène à faible teneur en thf

Publications (2)

Publication Number Publication Date
EP4004109A1 true EP4004109A1 (fr) 2022-06-01
EP4004109B1 EP4004109B1 (fr) 2024-08-21

Family

ID=67514293

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20743717.9A Active EP4004109B1 (fr) 2019-07-29 2020-07-27 Téréphtalate de polybutylène à faible teneur en thf

Country Status (6)

Country Link
US (1) US20220251291A1 (fr)
EP (1) EP4004109B1 (fr)
JP (1) JP7325605B2 (fr)
KR (1) KR20220043122A (fr)
CN (1) CN114174428B (fr)
WO (1) WO2021018848A1 (fr)

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1580834A (fr) 1968-01-04 1969-09-12
JPS5039599B2 (fr) 1973-03-30 1975-12-18
DE2407776A1 (de) 1974-02-19 1975-09-04 Licentia Gmbh Schaltung zur regelung der betriebsspannung fuer die transistor-zeilenendstufe eines fernsehempfaengers
DE2715932A1 (de) 1977-04-09 1978-10-19 Bayer Ag Schnellkristallisierende poly(aethylen/alkylen)-terephthalate
JPH06172506A (ja) 1992-12-03 1994-06-21 Polyplastics Co 改質ポリブチレンテレフタレート樹脂の製造方法
DE4401055A1 (de) 1994-01-15 1995-07-20 Basf Ag Verfahren zur Herstellung von thermoplastischen Polyestern mit niedrigem Carboxylendgruppengehalt
US6114495A (en) 1998-04-01 2000-09-05 Cargill Incorporated Lactic acid residue containing polymer composition and product having improved stability, and method for preparation and use thereof
JP2000154306A (ja) * 1998-11-18 2000-06-06 Toray Ind Inc ネジ挿入部位を有する成形品
JP3669480B2 (ja) * 2000-03-22 2005-07-06 東洋紡績株式会社 易成形性高光沢ポリエステル樹脂組成物
DE10155419B4 (de) 2001-11-12 2005-06-16 Inventa-Fischer Gmbh & Co. Kg Verfahren zur kontinuierlichen Herstellung von hochmolekularem Polyester sowie Vorrichtung zur Durchführung des Verfahrens
DE20320505U1 (de) 2003-09-17 2004-09-16 Coperion Werner & Pfleiderer Gmbh & Co.Kg Extruder zum Herstellen von syntaktischem Kunststoff
US8148489B2 (en) 2006-03-24 2012-04-03 E. I. Du Pont De Nemours And Company Thermoplastic resins containing PBT units, having reduced organic carbon emissions
DE102006025942B4 (de) 2006-06-02 2011-07-07 Uhde Inventa-Fischer GmbH & Co. KG, 13509 Verfahren zur kontinuierlichen Herstellung von hochmolekularen Polyestern durch Veresterung von Dicarbonsäuren und/oder Umesterung von Dicarbonsäuren mit Diolen und/oder deren Mischungen sowie Vorrichtung hierzu
MY157736A (en) * 2006-11-03 2016-07-15 Basf Se Low-emission polyester molding materials
DE102009020211A1 (de) 2009-05-07 2010-11-11 Basf Se Verwendung eines Polyesters zur Herstellung von Formteilen mit einem niedrigen Gehalt an extrahierbaren Verbindungen
DE102011109696A1 (de) 2011-08-06 2013-02-07 Daimler Ag Funktionalisiertes Innenraumverkleidungsbauteil und Verfahren zu dessen Herstellung sowie Kraftfahrzeug mit dem Innenraumverkleidungsbauteil
CN109535668A (zh) * 2012-03-30 2019-03-29 胜技高分子株式会社 聚对苯二甲酸丁二醇酯树脂组合物以及成型体
AU2014277109B2 (en) * 2013-06-07 2017-05-18 Basf Se Polyester molding compounds with low TOC emission
EP2816081A1 (fr) 2013-06-17 2014-12-24 Basf Se Masses de moulage en polyester avec faible émission de TOC
JP6668768B2 (ja) * 2015-01-30 2020-03-18 東レ株式会社 ポリブチレンテレフタレート樹脂組成物およびそれからなる成形品
JP2017036442A (ja) * 2015-08-12 2017-02-16 東洋紡株式会社 ポリエステル樹脂組成物、これを含む光反射体用部品および光反射体
EP3287493A1 (fr) 2016-08-26 2018-02-28 LANXESS Deutschland GmbH Compositions de polyester

Also Published As

Publication number Publication date
WO2021018848A1 (fr) 2021-02-04
KR20220043122A (ko) 2022-04-05
JP2022543575A (ja) 2022-10-13
EP4004109B1 (fr) 2024-08-21
CN114174428B (zh) 2023-07-18
JP7325605B2 (ja) 2023-08-14
US20220251291A1 (en) 2022-08-11
CN114174428A (zh) 2022-03-11

Similar Documents

Publication Publication Date Title
DE102011077447B4 (de) Verfahren zur Herstellung eines Formkörpers aus einer Polymilchsäure-Kompositzusammensetzung, Formkörper und Automobilteil
EP1871825A1 (fr) Matiere de moulage et elements de moulage en thermoplastique contenant des particules inorganiques nanometriques, procede pour realiser cette matiere de moulage et ces elements de moulage, et leurs utilisations
EP3356591B1 (fr) Procede de fabrication d'un semi-produit fibre/matrice
WO2008003309A2 (fr) Procédé d'identification de matières plastique
EP2719728A1 (fr) Masses de formage
EP4003691A1 (fr) Polybutylène téréphtalate à faible teneur en thf
EP4004109B1 (fr) Téréphtalate de polybutylène à faible teneur en thf
EP2461955B1 (fr) Production de corps moulés contenant des additifs
EP4004108A1 (fr) Polybutylène téréphtalate à faible teneur en thf
EP0081144A2 (fr) Produits semi-finis de forme plane et postformables à chaud en poly(téréphtalate d'éthylène) renforcé de fibres
EP2780420B1 (fr) Produit composite, procédé de fabrication d'un produit composite et son utilisation, et produit final
CN111087746A (zh) 一种汽车用轻质、低噪音abs复合材料及其制备方法
KR102682856B1 (ko) 분쇄성이 우수한 복합재료용 재생셀룰로오스계 섬유의 소수성 표면개질방법
JP7023048B2 (ja) マスターバッチ、樹脂成形品、マスターバッチの製造方法及び樹脂成形品の製造方法
Mills et al. Developing recycled carbon fibre reinforced material for sustainable additive manufacturing
DE102009042742A1 (de) Modifiziertes Polyterephthalat
DE102023129018A1 (de) Formgebungsverfahren zum Herstellen eines Formteils
DE102009005640B4 (de) Thermoplastische Formmasse und Formteile, Verfahren zu deren Herstellung und deren Verwendung
EP4083122A1 (fr) Particule en mousse polymère et son procédé de fabrication à base de polybutylène téréphtalate
CN114369313A (zh) 一种含有石墨烯-金属有机骨架吸附材料的车用改性聚丙烯复合材料及其制备方法
WO2012052476A1 (fr) Granulés et le procédé de fabrication

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20220228

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20240321

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20240517

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: ENVALIOR DEUTSCHLAND GMBH

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502020008958

Country of ref document: DE